Treatment of oil-in-water emulsions



Patented Apr. 11,v 1950 UNITED STATES PATENT OFFICE TREATMENT OF OIL-IN-WATER- EMULSIONS Ike D'. Hall, Baytown, Tex., assignor, by msne assignments, to Standard Oil l'ievelo'pme'n', Company, Elizabeth, N. J., a' corporation of Delaware Application November 3, 1948, ySerial No. 58,1-1'6 s claims. (c1. 2525-3220)' The present invention is directed to a method for recovering hydrocarbons and water from oilin-water emulsions. More particularly, the invention is directed to the resolution of oil-in- Water emulsions containing very small amounts of oil. The' invention is particularly directed to those oil-in-water emulsions containing from 2000 to 101,000 parts per million of oil'.

` In the catalytic conversion of hydrocarbonsx it is customary to heat hydrocarbons to a high temperature and to Contact them at the high temperature, which may range from 800 up *to about l500 with a catalyst to cause the desired vreaction to proceed. However, at these high temperatures in the range given, the converted hydrocarbons are in themselves quite ren active and unless their temperature is reduced rapidly, the converted hydrocarbons may undergo other conversion operations to form undesirable products. In order to eliminate reactions ofthis nature, it has been customary to cool converted hydrocarbons from a reaction Zone ofay catalytic conversion operation or a thermal conversion operation to a' temperature substantially below the conversi'on temperature. This cooling may be accomplished by indirect means; however, it is a usual practice' to reducey rapidly the temperature of converted hydrocarbons by contacting them inI secluencewith a so-calledquench oil at a much lower temperature' than the converted' hydrocarbons and toA 'follow the rst quenching' operation in which' the convertedt hydrocarbons areA contacted with the oill with a second quenching operation "in which the converted hydrocarbons are` further' cooled by con# ta'c'ting with water. These'two quenching" operau tions successfully'lower the' temperatures of the' converted hydrocarbonv safelyv past the temperature at which side reactions may occur. However, there is' one great disadvantage" to' these quenching' operations in' that the' converted h'y'- dr'o'carboris' are thoroughly admixed in sequence with oil and with water under conditions such that' relatively stable emulsions are formed. These emulsions' are of the oil-in-i'ate'r type and usually contain an amount of oil in the range from 2 0004 to -10,000'r'larts per million parts of the emulsion and are extremely stable, resisting e'f'- forts` to resolve the emulsion into component parts;` Such an emulsion is extremely unde-` sirable since valuable hydrocarbons are lost therein and the water is unsuitable for further use.

since it may cause destruction of animal andv iish life` The amount of oil present in the emulsiony is',- also suiii'cien-tto preventuse/of the' water inthe various" processing operations` such ,asin a feed' to a boiler.' It will thus be seen that the This' emulsion containss'ufcient amountsl of oil so that it cannot be discharged into streamsl 2 problem of resolving these emulsions is very serious.

It is, therefore, the. main object of the present' invention to provide a process in which oil-nwa'ter emulsions' are' resolved into their component parts.

Another object of the' present invention is' to provide a process for removing oil from emulsions of oil-in-water in which the oil is present in very small amounts in the range between 2000 and. 10,000 parts per million.

A still further object of the present invention is to recover valuable oil lost from catalytic and thermal conversion' operations employing oil and water quenching steps.

The present' invention may be described briefly as involving the adjustment of the pH of an oilin-water emulsion to a pH no greater than 6 following which the acidied emulsion in at least an equal amount is contacted with a light hydrocarbon having' from 3 to 7 carbon atoms in the molecule to' form an intimate admixture therewith at av temperature in the range between 100 to 200 F. The admixture is then allowed to settle under the influence of gravity to form water and hydrocarbon phases which areseparated and recovered. Thus, in accordance with the present invention, by acidifying an oil-in-water emulsion and contacting the acidified emulsio-n with a light All,

hydrocarbon, it is possible to remove substantially all of the oil from an oil-in-water emulsion containing a small amount of oil in the range from about 2000 to 10,000 parts per million.

It is indeed surprising that the combinatior'i steps of acidifying and. contacting with a light hydrocarbon should 4cause the separation of a stable emulsion of oil and water into its component parts since prior experience has shown that neither of the two steps'taken separately allows the' beneficial resultsY to be obtained` which the combined steps allow. Therefore, it is tobe emphasized that my invention is directed to the resolution ot oilV-in-water emulsions involving acidifying to. a pH less than 6 and contacting.y

with a light hydrocarbon in sequence.

The type of emulsions which may be successfully treated in accordance with the present invention may include emulsions of oil-in-Water suchk as emulsions of hydrocarbons boiling from 350 F. and upward, such as for example,l kerosene hydrocarbons, gas oil hydrocarbons, lubricating oil hydrocarbons, and crude oil hydrocarbons emulsied with-water.4 While a large number ofcrude loilscontain hydrocarbons having boiling points below 350' F.,it is tobe understood that thepresent invention has application.particularly to those emulsions of oil-in-water in which'r-e1a' tively heavy asvc'pposed torel'atively light hydrocarbone` are involved. Thus, while'crude oil-is a mixture of light and heavy hydrocarbons, the

heavy hydrocarbons impart the characteristics to the crude oil which cause formation of emulsions.

The light hydrocarbons which may be employed in the practice of the present invention will generally include those hydrocarbons having from 3 to 7 carbon atoms in the molecule or mixtures" thereof. For example, the saturated hydrocarbons such as propane, butanes, pentanes, hexanes, heptanes, and the like or mixtures thereof may be employed as the hydrocarbon treating reagent in the practice of my invention. Similarly, the olenic hydrocarbons` such as propylene, butylenes, pentylenes, hexylenes, heptylenes, and the like may also be used or mixtures thereof. Mixtures of the foregoing olefins and parafnic hydrocarbons also may be employed as a treating reagent in the practice of my invention. 'A' satisfactory i treating reagent may include a C4 hydrocarbon obtained from a catalytic conversion operation ing operation. Similarly, light hydrocarbon-fracsuch as a dehydrogenation operation or a oral:-

tions from thermal treatments may also be employed. As a general rule, it may be state-fi that light hydrocarbons boiling below about 120 F.

and usually considered below the gasoline boil.

ing range will form the preferred treating rea-v gents in the practice of my invention.

The acid employed. in acidifying the emulsion to a pH below 6 and preferablyrin the range b`epropane is employed, it will be desirable to use a temperature in the lower Dart of the ran-fre whereas if butano or the higher hydrocarbons illustrated are employed, higher temperatures in the range given may be used. For example, if C4.. fraction is employed, it will be desirable to emf ploy a temperature from about 150 to about 200iJ F. with a preferred temperature range from about' 180 to 200 F.

`pressures employed in the treating operation in accordance with my invention will depend, of course, on the hydrocarbon employedas a contacting medium. As a general rule, it .may be stated that a pressure sufcient to maintain a liquid phase will be necessary.

It will be desirable to contact the ac"dified'l` emulsion with an amount of light hydrocarbon in the range from about l part of hydrocarbon `to one part of emulsion to 1 part of hydrocarbon to 10 parts of emulsion. Ordinarily, however, an amount of hydrocarbon suicient to provide a ratio of one part of hydrocarbon to three parts of emulsion will give satisfactory results.

'The invention will be further iuustrad by reference to the drawing in which Fig 1 is a flow diagram of lone embodiment of my invention in which an emulsion of oil-in-water is resolved into its component parts; and Y Fig. 2 is another embodiment of my invention in which an emulsion from a conversion operation is treated for recovery of the component parts thereof. Referring now to the drawing, and particularly to" Eig. 1, numeral II designates ja .charge line v4 through which an emulsion is introduced from a source not shown. This emulsion may be an emulsion of a hydrocarbon having a boiling point above about 350 F. and may include kerosene. gas oil, lubricating oil, or even crude oil and water. The emulsion in its passage through line II has admixed with it from line I2, controlled by valve I3, from a source not shown, a sufhcient amount of a mineral acid, such as sulfuric acid, to acidify the emulsion to a pH no greater than 6 and in the range from about 3.5 to 6. The acidiiiecl emulsion in line II then has admixed with it from line I4 controlled by valve I5 an amount of a light hydrocarbon, from a source not shown, boiling below the gasoline boiling range and having from 3 to 7 carbon atoms in the molecule. The amount of hydrocarbon introduced by line I4 into line I I may be an amount ranging from an equal amount of hydrocarbon to that of the emulsion to an amount substantially less than the emulsion. For

example, the amount of emulsion to hydrocarbon "V discharged into an incorporator I6 in which the to 1 with a preferred amount of about 3 to 1.

The admixture in line I I to which sulfuric acidr and light hydrocarbon have been added is then admixture is intimately contacted and from thence it passes by line I'I into a heater I8 where its temperature is adjusted to a temperature in the range between 100 to 200 F. It may be desirable, however, under some conditions, to

locate heater I8 in line II immediately ahead of' the incorporator. The heated admixture then discharges from heater I8 by line I9 into a settling vessel or separator 20 which is of sufficient capac-v in accordance with the present invention, sepa' rates into a hydrocarbon layer and a water layer'v in separator 20 which are removed by lines 2| and 22, respectively. The hydrocarbon phase may.

then be subjected to distillation for recovery of the light hydrocarbon for reuse and for recovery of the desired heavy hydrocarbons, while the water phase may be separately withdrawn and employed further in processing operations such as a feed to a steam generation plant, the oil con.- tent of the water having been reduced to a low.

gure of the order of less than 5 parts per million.

Referring now to Fig. 2, a vaporlzed, converted hydrocarbon fraction containing water vapor.

such as a converted hydrocarbon from a butylenes dehydrogenation plant, is introduced into the, system by line 30 and discharged thereby into,

an oil quench tower 3| into which is introduced by line 32 a quench oil which may be an oil boiling in the gas oil boiling range although lighter4 and heavier oils than gas oilhhydrocarbons may; be employed. The quench oil reduces the temper- `1 Aature of the converted hydrocarbons from about 540 F. to about 210 F., the temperature o f the? converted hydrocarbon having been reduced from f about 1150 F. to about 54ml.- prior to 'introduce4v tion into the quench tower 3I by passage through--A a waste heat boiler. The quench oil and dissolved; hydrocarbons are removed from quench tower 3| by line 33 and are routed thereby to strippingsince they dof not form an essentia1- part of lmy ir'ivention'.l y t' and -absorbing facilities'no'tshown will sufce to say that the oil withdrawn by line about 170 F. The cooled products then discharge by line into a separator 31 from whenceemulsion is withdrawn by line 38, which is treated in` a manner to be described, and hydrocarbon by line 39 which discharges the hydrocarbon stream into a water quench tower 40. Introduced into water quench tower 40 by line 4| Ais a stream of water which causes the further cooling of the hydrocarbons introduced into tower 40 by line 39. The hydrocarbons discharge from thevtop of quench tower 40 by line 42 and are then routed to hydrocarbon recovery facilities, not shown, which may include compression, absorption, and stabilization facilities, the oil withdrawn from tower 3l by line 33, after suitable stripping, being employed as an absorption oil for the non-con densible hydrocarbons withdrawn from tower 40 by line 42.

Water containing emulsified hydrocarbons in the amount in the range between 2000 to 10,000 parts per million is withdrawn from the bottom of ltower 40 by line 43 and is separated into two portions, one portion being routed to the top of the tower by line 44 containing cooler 44a which connects into line 4| and the second portion being discharged by line 43 in admixture with the emulsion from line 38 into incorporator 45. After admixture with sulfuric acid, which is introduced by line 46 controlled by valve 41, from a source not shown, in an amount sufficient to adjust the acidity to a pH no greater than 6 and after admixture with a light hydrocarbon of thetype illustrated through line 48 controlled by valve 49, from a source not shown, in an amount sufcient to provide from 1 to 10 parts of acidiiied emulsion for every part of light hydrocarbon, the mixture of oil, water, and light hydrocarbon is then discharged into incorporator 45.

The temperature of the stream passing through line 43 is in the range from about 150 to 200 and this acidied stream containing ,hydrocare bons which are added as described passes through incorporator and is intimately admixed therewith. After the admixture of hydrocarbons and emulsion passes through incorporator 45, it dischargesby line 50 into a separator 5l which is of suiiicient capacity to provide a suflicient residence time for separation of the emulsion into a hydrocarbon phase which is withdrawn by line 52 and a water phase which is withdrawn by line 53.

The hydrocarbon discharged by line 52 may be further treated to separate light hydrocar` bons therefrom and to recover same for further use as may be desired or for recycling tothe process and for the recovery of the hydrocarbon component of the emulsion. The waterv phasevdis-- charges by line 53 into a water stripping tower 54 to which is introduced by line 55a sufficient amount of steam to cause stripping from the water phase in tower 54 of light hydrocarbons which may have dissolved in the water. These light hydrocarbons and water vapor rnay be withdrawn from the stripping tower 54'zjbly line 5S. Substantially oil-free water suitable 'for boiler feed water orv other uses may be.rc-".covered"fromj tower 54 by line 51. This stream may contain less than 5 parts per million of oil whereas the stream passing through line 43 may contain from 2000 to 10,000 parts per million of oil.

rEhe invention will be further illustrated by the following examples.

A water condensate from a lion of emulsied oil Was acidiiied to a pH of `6 with sulfuric acid. Three parts of this con-VVA ing a pH in the range from 8 to 9 was separated into 4 portions. The first portion was acidied by addition of sulfuric acid thereto to a pH in the range between 3.5 to 4.5 and allowed to settle under the influence of gravity for 4 hours. The water phase was analyzed for oil content and found to contain'20 to 30 parts per million.

The second portion was acidied to a pH of 5 and allowed to settle for 15 minutes under the influence of gravity. The separated water phase was analyzed and found to contain between 1500 and 2000 parts per million of oil.

The third portion having a pH in the range from 8 lo 9 was washed with a C4 hydrocarbon fraction and allowed to settle for 15 minutes without' adjustment of the pI-I. The water phase was found to contain between 2000 and 2500 parts per million of oil.

The forth portion had added to it a suiiicie'nt amount of sulfuric acid to adjust the acidity to a pH of 5 and was then washed with the same C4 hydrocarbon fraction to which the third portion was subiected. vThis fourth portion was a1- lowed to settle for 15 minutes. The water phase was then tested and found t'o contain less'than 5 parts per million of oil.

These data show that pH adustrnent followed by l5 minute settling time without the hydrocarbon wash step reduces the oil content from 3000 parts per million to between 1500 and 2000 parts per million. Washing three parts of the emulsion with 1 part of the hydrocarbon without adjustment of pI-I reduced the oil content to between 2000 and 2500 parts per million after 15 minutes settling time, whereas the combined steps of pH adjustment and -hydrocarbon Wash for' the" sarne settling time of 15 minutes reduced the oil content to less than 5 parts per million, a wholly unexpected result. These data show conclusively the superiority of the combined process over the individual steps of the prior art.

The present invention has particular application to butylenes dehydrogenation processes wherein butadiene is manufactured by dehydrogenation of normal butylenes over a fixed catalyst bed in the presence of large quantities of steam. The reaction is carried out at a temperature in the range between 1100 to 1200615. and', consequently, the reactant mixture must be quenched to a lower temperature as rapidly as possible. This isaccomplshed by passing the reactor effluent through waste heat boilers which 're-'- duces the temperature of the effluent to about butylenes dehy drogenation unitl containing 3000 parts per mil#- asegura,

$409,131.- `p to' this point, little. or no condensation-of the steam takes place, and under the conditions existing in the oil quench towel", there is lafcertain amount of quench oil carried out with the entrained quench oil to form an ex-y tremely-stable emulsion of oil and water. The oil-content amounts to approximately3000 to 9000 parts per million, but may be slightly less or slightly greater. Prior to my invention, light hydrocarbons were removed and the residual water, still containing appreciable quantities of oil, was discharged from theunit, the waterv being of little further use.A In accordance with my invention, sulfuric acid is added to the emulsion before the latter is stripped of light hydrocarbons in an amount suicient to adjust the pl-Il to -6 or less and the acidied mixture is admixed with a light fraction, such as a C4 hydrocarbon fraction recovered in the process. The admixture.

covery of the light hydrocarbons and the hydro-` carbons removed from the emulsion. My invention results in economies by recovery of valuablev oil and water and by eliminating a nuisance which might result from discharge of Water containing an appreciable amount of oil into streams and other natural bodies of water.

.The nature and objects of the present invention having been completely described and illustrated,l

what Iwish to claim as new and useful and to secure by Letters Patent is:

1. A method for breaking an emulsion of oil inl water which comprises adjusting the pH of said emulsion to a pH no greater than 6.0, admixing said acidied emulsion in at least equal amounts with ahydrocarbon having from 3 to '7 carbonv atoms in the ymolecule sufficient to cause phase separation, settling the admixture to form a hydrocarbon phase and a water phase, and recovering said phases.

-, 2. A method in accordance with claim l in4 which the pH of the emulsion is adjusted by adding a mineral acid thereto.

3. A method for breaking an emulsion of oil in water which comprises admixing said emulsion at a temperature in the range between 100 and 200 F. with a suiiicient amount of a mineral acid .to acidifysaid emulsion to a pH no greater' than 6.0, admixing said acidified emulsion in at,

leastl equal amounts with a light hydrocarbon having from ,3 to 7 carbon vatoms in the molecule sufcient'to cause phase separation, settling the` admlxtureto form a hydrocarbon phase and a,

water phase, and recovering said phases.

4. A method in accordance with claim 3 in which the mineral acid is sulfuric acid.

' 5. A method for breaking an aqueous emulev sion containing an amount-of oil in the range between 2000 andl 10,000 parts -per million of the emulsion which comprises adjusting the pH of said emulsion to a pH no greater than 6.0, 'ad.

mixing said acidiiied emulsion with a light hydrocarbon having from 3 to 7 carbon atoms in the molecule in an amount in the ratio between lil and 1:10, settling the admixture under they influence of gravity to form a hydrocarbon phase and a water phase, and recovering said phases.

- 6. A method for breaking an emulsion containing an amount of oil in the range from 2000 to 10,000 parts per million based on the emulsion,

admixing said emulsion at a temperature in thef range between 100 and 200 F. with a sunicient.

amount of a mineral acid to acidify said emulsion to a -pI-I in the range between 3.5 and 6, ad-

mixingsaid acidied emulsion with an amount' of a light hydrocarbon having from 3 to 'l carbon atoms in the molecule to provide an admixture containing approximately 3 parts of emulsion and 1 .part of hydrocarbon, settling the admixtureunder the iniiuence of gravity to form a hydrocarbon phase and a water phase, and recovering said phases.

7. A method for separating oil from a mixture of converted hydrocarbons and water consisting predominantly of water and oil in the range between 2000 and 10,000 parts per million which comprises adding sulfuric acid to said admixture in vanamount suiilcient to adjust the pI-I of the. admixture to approximately 5, admixing thev acidied admixture with a suiicient amount of alight hydrocarbon boiling below the gasoline boiling range to provide a second admixture containing approximately 1 part of hydrocarbon and 3 parts of acidied admixture, maintaining the temperature of the second admixture at a temperature in the range between 100 to 200 F., settling the second admixture to form a hydrocarbon phase and a water phase, and separately recovering said phases.

. 8. Amethod for separating oil from a mixtuure of converted hydrocarbons and water containing an amount of oil in the range between 2000 and 10,000 parts per million, said oil boiling in the gas oil boiling range, which comprises adding a sufiicient amount of sulfuric acid to said admixture to acidify said admixture to a pH of approximately 5, admixing said acidied admixture with a hydrocarbon fraction having 4 carbon atoms in the molecule in an amount of one part of hydrocarbon fraction to 3 parts of acidifed admixture to form a second admixture, maintaining the temperature of the second admixture at a temperature in the range between 150 to 200 F.,

settling the admixture to form a hydrocarbon phase and a water phase, and separately recover-' A ing said phases.

IKE D. HALL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date y '1,247,782 Ayres Nov. 27, 1917' 2,235,639 v4Koch Mar. 18, 1941'v 2,326,882 Perdew Aug. 17, 194:3` 2,366,792 Kirkbride Jan. 9, 1945 2,383,363 Batchelder ---1---- Aug. 21, 1945' 2,431,526 Viles Nov. 25, 1947 

1. A METHOD FOR BREAKING AN EMULSION OF OIL IN WATER WHICH COMPRISES ADJUSTING THE PH OF SAID EMULSION TO A PH NO GREATER THAN 6.0, ADMIXING SAID ACIDFIED EMULSION IN AT LEAST EQUAL AMOUNTS WITH A HYDROCARBON HAVING FROM 3 TO 7 CARBON ATOMS IN THE MOLECULE SUFFICIENT TO CAUSE PHASE SEPARATION, SETTLING THE ADMIXTURE TO FORM A HYDROCARBON PHASE AND A WATER PHASE, AND RECOVERING SAID PHASES. 